Analysis and residue levels of forchlorfenuron (CPPU) in watermelons

This paper describes the application of liquid chromatography-tandem mass spectrometry (LC/MS-MS) for analysis of residues of forchlorfenuron (CPPU), a new plant growth regulator, in watermelons, after a sample preparation step based on the buffered Quick, Easy, Cheap, Effective, Rugged and Safe extraction method. Analytical determinations were carried out in a triple quadrupole system fitted with an electrospray interphase operating in the positive ionisation mode (ESI+). Three simultaneous MS-MS transitions of the quasi-molecular ion m/z 248 (precursor ion) were monitored for data acquisition (248 > 129, 248 > 155, and 248 > 248), using the transition 248 > 129 for quantitation. Recovery studies on watermelons at levels of 1-200 microg/kg, performing five replicates at each level and using bracketing single-level calibration with matrix-matched standards for quantitation, gave forchlorfenuron mean recoveries ranging from 82 to 106% with relative standard deviations (RSD) lower than 18%. The limit of determination was established at 1 microg/kg. The method was applied to evaluate the persistence of forchlorfenuron residues in watermelons grown in plastic greenhouses, after applying an individual spray treatment to the flower ovary at the anthesis stage (45 mu g/flower and 60 mu g/flower for cv "Extazy" and cv "reina de corazones" watermelons, respectively). One month after treatment, 20 "Extazy" watermelon units (1.5-2 kg/unit) and 20 "Reina de corazones" watermelon units (4-5 kg/unit) were collected and analyzed individually. None of the samples contained forchlorfenuron residues higher than 1 microg/kg.     

Heavy metals in untreated/treated urban effluent and sludge from a biological wastewater treatment plant

Background, Aim and Scope

The presence of heavy metals in wastewater is one of the main causes of water and soil pollution. The aim of the present study was to investigate the removal of Cd, Cu, Pb, Hg, Mn, Cr and Zn in urban effluent by a biological wastewater treatment, as well as to quantify the levels of As, Be, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sn, Tl, V and Zn in dewatering sludge from the Biological Wastewater Treatment Plant to Ribeirão Preto (RP-BWTP), Brazil.

Materials and Methods

Concentrations of Cd, Cr, Cu, Mn and Pb in wastewater and those of Ni in sludge were determined by atomic absorption spectrophotometry with graphite furnace atomization. Mercury concentrations in wastewater were measured by hydride generation atomic spectrophotometry, and Zn levels were determined by atomic absorption spectrophotometry using acetylene flame. In sludge, the levels of As, Be, Cd, Cr, Cu, Fe, Hg, Mn, Pb, Sn, Tl, V and Zn were determined by inductively coupled plasma-mass spectrometry.

Results

The percentages of removal efficiency (RE) were the following: Hg 61.5%, Cd 60.0%, Zn 44.9%, Cu 44.2%, PB 39.7%, Cr 16,5% and Mn 10.4%. In turn, the mean concentrations (mg/kg) of metals in dewatering sludge followed this increasing order: Tl (<0.03), Hg (0.31), Be (0.43), As (1.14), Cd (1.34), V (59.2), Pb (132.1), Sn (166.1), Cr (195.0), Mn (208.1), Ni (239.4), Cu (391.7), Zn (864.4) and Fe (20537).

Discussion

The relationship between metal levels in untreated wastewater, as well as the removal efficiency are in agreement with previous data from various investigators, It is important to note that metal removal efficiency is not only affected by metal ion species and concentration, but also by other conditions such as operating parameters, physical, chemical, and biological factors.

Conclusions

Metal values recorded for treated wastewater and sludge were within the maximum permitted levels established by the Environmental Sanitation Company (CETESB), São Paulo, Brazil.

Recommendations

There is an urgent need for the authorities who are responsible for legislation on sludge uses in agriculture of establishing safety levels for As, Be, Hg, Sn, Tl and V.

Perspectives

According to the current metal levels, RP-BWTP sludge might be used for agriculture purposes. However, for an environmentally safe use of sewage sludge, further studies including systematic monitoring are recommended. Annual metal concentrations and predicted variations of those elements in the sludge should be monitored.

     

Discriminating the pH toxicity to Poecilia reticulata Peters, 1859 in the Dunas Lake (Camaçari, BA, Brazil)

Toxic potential of the pH reduction to fingerlings of Poecilia reticulata, through acute toxicity bioassays, as well as the influence of increased pH on the toxicity were assessed. Acid lake samples (Dunas Lake) were collected during 19 months, and assessed with following treatments: water at local pH (+/-3.0) and samples with modified pH to 3.5, 3.8, 4.0, 4.3, 4.6, 5.0, 5.5, 6.0, and 6.5. Culture water samples with pH reduced to 3.0 were also assessed. Newborn P. reticulata were exposed during 96h, and dead/immobile organisms were counted at various time intervals during exposure (short intervals in the beginning and long towards the end). Mean results of LT(50) and confidence intervals from the Dunas Lake and control water with reduced pH were 1.36 (+/-0.48)h, and 1.03 (+/-0.50)h, respectively, with no statistical difference. Samples with increased pH showed a significant reduction in toxicity, with no toxicity detected at pH 6.0 and higher. Relationship between pH and lethal toxicity for fingerlings of P. reticulata demonstrated that pH exerted a strong effect on the survival of this species at the Dunas Lake, explaining about 80% of the toxicity observed.     

Inverse modeling of multicomponent reactive transport through single and dual porosity media

Compacted bentonite is foreseen as buffer material for high-level radioactive waste in deep geological repositories because it provides hydraulic isolation, chemical stability, and radionuclide sorption. A wide range of laboratory tests were performed within the framework of FEBEX (Full-scale Engineered Barrier EXperiment) project to characterize buffer properties and develop numerical models for FEBEX bentonite. Here we present inverse single and dual-continuum multicomponent reactive transport models of a long-term permeation test performed on a 2.5 cm long sample of FEBEX bentonite. Initial saline bentonite porewater was flushed with 5.5 pore volumes of fresh granitic water. Water flux and chemical composition of effluent waters were monitored during almost 4 years. The model accounts for solute advection and diffusion and geochemical reactions such as aqueous complexation, acid-base, cation exchange, protonation/deprotonation by surface complexation and dissolution/precipitation of calcite, chalcedony and gypsum. All of these processes are assumed at local equilibrium. Similar to previous studies of bentonite porewater chemistry on batch systems which attest the relevance of protonation/deprotonation on buffering pH, our results confirm that protonation/deprotonation is a key process in maintaining a stable pH under dynamic transport conditions. Breakthrough curves of reactive species are more sensitive to initial porewater concentration than to effective diffusion coefficient. Optimum estimates of initial porewater chemistry of saturated compacted FEBEX bentonite are obtained by solving the inverse problem of multicomponent reactive transport. While the single-continuum model reproduces the trends of measured data for most chemical species, it fails to match properly the long tails of most breakthrough curves. Such limitation is overcome by resorting to a dual-continuum reactive transport model.     

Particulate matter levels in a South American megacity: the metropolitan area of Lima-Callao,Peru

The temporal and spatial trends in the variability of PM₁₀ and PM_2.5 from 2010 to 2015 in the metropolitan area of Lima-Callao, Peru, are studied and interpreted in this work. The mean annual concentrations of PM₁₀ and PM_2.5 have ranges (averages) of 133–45 μg m^?3 (84 μg m^?3) and 35–16 μg m^?3 (26 μg m^?3) for the monitoring sites under study. In general, the highest annual concentrations are observed in the eastern part of the city, which is a result of the pattern of persistent local winds entering from the coast in a south-southwest direction. Seasonal fluctuations in the particulate matter (PM) concentrations are observed; these can be explained by subsidence thermal inversion. There is also a daytime pattern that corresponds to the peak traffic of a total of 9 million trips a day. The PM_2.5 value is approximately 40% of the PM₁₀ value. This proportion can be explained by PM₁₀ re-suspension due to weather conditions. The long-term trends based on the Theil-Sen estimator reveal decreasing PM₁₀ concentrations on the order of ?4.3 and ?5.3% year^?1 at two stations. For the other stations, no significant trend is observed. The metropolitan area of Lima-Callao is ranked 12th and 16th in terms of PM₁₀ and PM_2.5, respectively, out of 39 megacities. The annual World Health Organization thresholds and national air quality standards are exceeded. A large fraction of the Lima population is exposed to PM concentrations that exceed protection thresholds. Hence, the development of pollution control and reduction measures is paramount.     

Evaluation of metals in several varieties of sweet potatoes (Ipomoea batatas L.): comparative study

Sweet potatoes are a staple in the diet of some people and an excellent source of minerals. Metal monitoring in food, like sweet potatoes, provides basic information on safety aspects in regulatory processes as well as nutritional values. One hundred five samples of three varieties of sweet potatoes were randomly obtained from supermarkets, farmers markets, and farmers' plots in Tenerife (Canary Islands, Spain). The edible portion (pulp) was the only part considered for analysis. Flame atomic absorption spectrometry was used to determine the contents of sodium (Na), potassium (K), calcium (Ca), magnesium (Mg), copper (Cu), iron (Fe), manganese (Mn), and zinc (Zn), while the levels of chromium (Cr), nickel (Ni), cadmium (Cd), and lead (Pb) were determined using graphite furnace atomic absorption spectrometry. The mean concentrations were 500 Na, 4409 K, 564 Ca, 609 Mg, 1.291 Cu, 6.554 Fe, 2.324 Mn, 2.348 Zn, 0.028 Cr, 0.048 Ni, 0.001 Cd, and 0.003 Pb mg/kg, respectively. Potassium presented the highest contents in all varieties of sweet potatoes. Iron was the most abundant microelement. The orange fleshed sweet potato variety offered greater nutritional contributions to the recommended intakes than the rest of the varieties studied. The estimated mean daily intake of Ni (0.72 mg/day) detected in our samples was highly consistent with other studies. Average daily intakes of Cd (0.015 μg/day) and Pb (0.045 μg/day) were below toxicological reference values. In conclusion, the levels of Cd and Pb detected in the sweet potatoes analyzed do not represent any toxicological risk to consumers.     

Foraminiferal biotopes and their distribution control in Ria de Aveiro (Portugal): a multiproxy approach

Ria de Aveiro, which is located in the centre of Portugal (40° 38′ N, 8° 45′ W), is a well-mixed and complex coastal lagoon that is separated from the sea by a sandy barrier and connects with the Atlantic through an artificial inlet. Tidal currents are the main factor controlling the lagoon’s hydrodynamics and, to a great extent, the sedimentary dynamic. The inner lagoonal zones receive input from several rivers and experience the pressure caused by the accumulation of organic matter and pollutants (namely, trace metals) from diverse anthropic activities. This paper is the first piece of work aiming to recognize, characterize and explain the main benthic foraminiferal biotopes in Ria de Aveiro. To provide a broad overview of this kind of setting, our results are compared to those of previous published studies conducted in similar transitional environments. The research is based on an investigation of 225 sites spread throughout this ecosystem. Utilizing a statistical approach, this study analyses the details of dead benthic foraminiferal assemblages composed of 260 taxa, the texture and composition (mineralogical and geochemical) of the sediment and physicochemical data. On the basis of the results of R-mode and Q-mode cluster analyses, several different biotopes can be defined as marsh biotope/near-marsh biotope; marginal urban/marginal urban mixing biotope; inner-outer lagoon biotope or enclosed lagoon; outer lagoon biotope, mixed sub-biotope; and outer lagoon, marine sub-biotope. These biotopes are related to foraminifera assemblages and substrate type and are influenced by local currents, water depth, chemical and physicochemical conditions, river or oceanic proximity, and anthropogenic impact, as evidenced by the mapping of the six factor loadings of the principal component analysis conducted herein. Based on a similar methodology of analysis as that applied in previous studies in the Lagoon of Venice, comparable biotypes were identified in Lagoon of Aveiro.     

A methodology to identify representative configurations of sensors for monitoring soil moisture

Soil moisture is the key link among hydroecological compartments, responding dynamically to sequences of atmospheric processes and management conditions and modulating physical, chemical, and biological processes in the soil. Currently, there are a variety of monitoring techniques to measure, directly or indirectly, the soil moisture. However, some practical issues remain open like the definition a priori of the number, location and depth of the monitoring points, and the impact of failing or poor performance soil moisture sensors. Here, we present a set of techniques, namely Δθ time series, wavelet filtering, and time stability, to identify representative points and monitoring depths through an analysis of hourly soil moisture time series for different configuration of the monitoring network. We used real data from a monitoring network consisting of seven monitoring points, each one with four EC-5 probes (Decagon Devices Inc., Pullman, WA) at 20, 40, 60, and 100?cm. The use of simple time series of Δθ allowed us to assess the spatiotemporal influence of the monitoring points, while the wavelet periodograms allowed us to get insight about the response of the monitoring points at different time scales. Both methods are easy to implement or adapt to specific conditions, being coherent to the results derived from time stability analysis. For our case study, we concluded that we could reallocate 16 sensors (out of 28) without a significant loss of information. However, the final decision strongly relies on a deep knowledge of the site features and the objectives of the monitoring network.